Oxygen Scavenger Compositions for Completion Brines

ABSTRACT

An oxygen scavenger for completion brines effective and stable in high temperature subterranean formations. In one embodiment, the scavenger contains erythorbate and alkylhydroxlyamine.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to compositions for removing dissolvedoxygen from drilling and completion fluids for use in high temperaturesubterranean formations.

2. Description of Relevant Art

Completion operations normally include perforating the casing andsetting the tubing and pumps prior to, and to facilitate, initiation ofproduction in hydrocarbon recovery operations. The various functions ofdrill-in, completion and workover fluids include controlling wellpressure, preventing the well from blowing out during completion orworkover, and preventing the collapse of the well casing due toexcessive pressure build-up. The fluid is meant to help control a wellwithout damaging the producing formation or completion components.Specific completion fluid systems are selected to optimize the wellcompletion operation in accordance with the characteristics of aparticular geological formation. “Drill-in” drilling fluids, used indrilling through a producing zone of a hydrocarbon bearing subterraneanformation, and completion fluids, used in completing or recompleting orworking over a well, are typically comprised of clear brines. As usedherein, a “producing zone” is understood to be a portion of ahydrocarbon bearing subterranean formation that contains hydrocarbons,and thus a wellbore penetrating such portion of the formation is likelyto receive hydrocarbons from the zone for production. A “producing zone”may alternatively be called a “production zone” or a “pay zone.”

Seldom is a regular drilling fluid suitable for completion operationsdue to its solids content, pH and ionic composition. Drill-in fluidscan, in some cases be suitable for both drilling and completion work.Fluids can contain suspended solid matter consisting of particles ofmany different sizes. Some suspended material will be large enough andheavy enough to settle rapidly to the bottom of a container if a liquidsample is left to stand (the settable solids). Very small particles willsettle only very slowly or not at all if the sample is regularlyagitated or the particles are colloidal. These small solid particlescause the liquid to appear turbid (i.e., cloudy or hazy). The potentialof particle invasion and/or filter cake buildup to damage a formation byreducing permeability in the producing zone has been recognized for manyyears. If permeability gets damaged, it cannot be 100 percent restoredby any means. Loss in permeability means a decrease in anticipatedproduction rates and ultimately in a decrease in production overall.

Thus, the importance of using clear completion and workover fluids tominimize formation damage is now well recognized and the use of clearheavy brines as completion fluids is now widespread. Most such heavybrines used by the oil and gas industry are calcium halide brines,particularly calcium chloride or calcium bromide brines, sodium halidebrines, particularly sodium chloride or sodium bromide, or formatebrines.

As used herein, the terms “completion fluids” and “completion brines”shall be understood to be synonymous with each other and to includedrill-in and workover fluids or brines as well as completion fluids orbrines, unless specifically indicated otherwise.

Completion brines often contain dissolved and entrained air which entersthe brines as it is circulated through the drill string into the wellbore penetrating a subterranean formation. The presence of oxygen fromthe air in the brines drastically increases the rate of corrosion anddeterioration of metal surfaces in the drill string, casing andassociated equipment as compared to such fluids which do not containoxygen. To minimize such corrosion, and the presence of oxygen,completion brines are frequently treated with oxygen scavengers.

Generally, oxygen scavengers used in completion brines are reducingagents that will react out most of the oxygen dissolved in the brine.Common oxygen scavenger chemistries include sulfites, hydrazine, anderythorbate. Sulfites are not generally used in completion brinesbecause the oxidized product, sulfate, can precipitate and lead to otherforms of corrosion.

A preferred oxygen scavenger for completion brines is sodiumerythorbate, because it reduces the oxygen concentration in a variety ofcompletion brines without causing precipitation seen with sulfites.However, erythorbate tends to decompose at elevated temperatures. Attemperatures of about 275° F. and higher, sodium erythorbate in brinedecomposes resulting in transformation of the brine from a desired clearand colorless fluid to an undesired dark, brown opaque fluid. Thistransformation of the brine is troublesome as it gives rise to concernsthat the brine may be potentially corrosion-inducing or damaging to theformation. As used herein, “clear and colorless” with respect to brineor completion fluids means that the fluid has an “NTU” (nephelometricturbidity unit) less than about 20. NTU is an American PetroleumInstitute accepted unit related to the suspended solids in a brine(higher NTU=more suspended solids), based on how much light is scatteredby a sample. The procedure for determining NTU is described in API RP13J, “Testing of Heavy Brines,” incorporated herein by reference, and isa procedure well known to those of ordinary skill in the art.

Thus, while there are a number of oxygen scavengers for drilling fluidsin the marketplace, there continues to be a need for oxygen scavengershaving utility in completion brines for use at high temperatures.

SUMMARY OF THE INVENTION

According to the invention, dissolved oxygen is removed from an aqueousfluid, particularly a completion fluid or brine, by contacting theaqueous oxygen-containing fluid with an oxygen scavenger comprisingerythorbate and alkylhydroxylamine. This oxygen scavenger is effectiveeven at high temperatures, and does not break down or result in thediscoloration of the fluid or transformation of the fluid from, forexample, clear and colorless, to dark and opaque. The invention includesa completion fluid for use in high temperature subterranean formationsthat comprises a clear, colorless brine and an erythorbate andalkylhydroxylamine oxygen scavenger, and a method of completing awellbore in such a subterranean formation employing such a completionfluid. In the invention, erythorbic acid, ascorbic acid or ascorbate maybe substituted for erythorbate.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph comparing the removal of dissolved oxygen from a 9.5lb/bbl sodium chloride brine over a 24 hour period at room temperatureby 0.5 lb/bbl oxygen scavenger of the invention and by 0.5 lb/bbl oxygenscavenger consisting of erythorbate.

FIG. 2 is a graph comparing the removal of dissolved oxygen from a 12.5lb/bbl sodium bromide brine over a 24 hour period at room temperature by0.5 lb/bbl oxygen scavenger of the invention and by 0.5 lb/bbl oxygenscavenger consisting of erythorbate.

FIG. 3 is a graph comparing the removal of dissolved oxygen from a 11.0lb/bbl calcium chloride brine over a 24 hour period at room temperatureby 0.5 lb/bbl oxygen scavenger of the invention and by 0.5 lb/bbl oxygenscavenger consisting of erythorbate.

FIG. 4 is a graph comparing the removal of dissolved oxygen from a 15.5lb/bbl zinc bromide/calcium bromide brine over a 24 hour period at roomtemperature by 0.5 lb/bbl oxygen scavenger of the invention and by 0.5lb/bbl oxygen scavenger consisting of erythorbate.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

The present invention provides an oxygen scavenger for aqueouscompletion fluids that is effective at reducing the level of oxygen inthe fluid during a completion operation even at high temperatureswithout causing problematic precipitation or discoloration of the fluid.

The oxygen scavenger of the invention comprises a blend of erythorbateand alkylhydroxylamine. Without wishing to be limited by theory, it isbelieved that the alkylhydroxylamine and erythorbate blended togetherfor use in the completion fluid, which is most preferably a clear andcolorless brine, have a synergistic effect in the fluid, wherein thealkylhydroxylamine imparts stability to the erythorbate at hightemperatures. At temperatures encountered in a subterranean formation ofabout 275° F. or higher, even as high as 500° F., the erythorbate in theoxygen scavenger of the invention does not appear to break down—thecompletion brine remains clear and colorless. The alkylhydroxylamine, aswell as the erythorbate, is believed to be scavenging oxygen.

Any alkylhydroxylamine is believed suitable for use in the presentinvention. Examples include, without limitation, isopropylhydroxylamine,diethylhydroxylamine, tert-butylhydroxylamine, phenylhydroxylamine,cyclohexylhydroxylamine, and benzylhydroxylamine. The many possibilitiesfor the various alkylhydroxylamines that may be used is appreciated fromthe following example structures:

Erythorbic acid, ascorbic acid or ascorbate may be substituted forerythorbate in the invention.

An experiment was conducted where 1.0 lb/bbl oxygen scavenger of theinvention containing a blend of about 10% w/w erythorbate (0.1 lb/bbl)and 90% w/w alkyhydroxylamine solution (0.9 lb/bbl) was added to samplesof 9.5 lb/gal sodium chloride brine, and compared to brine samplescontaining 0.5 lb/bbl erythorbate alone as an oxygen scavenger. Thesamples containing the scavenger of the invention remained clear andcolorless, even after aging for as much as 16 hours at 300° F., 400° F.,and even 500° F. The samples containing the scavenger consisting only oferythorbate, turned opaque and brown. The experiment was repeated withthese oxygen scavengers in an 11.0 lb/gal calcium chloride brine and ina 15.5 lb/gal calcium bromide/zinc bromide brine and the same resultswere seen. The brine samples containing the scavenger of the inventionremained clear and colorless at 300° F., 400° F., and even at 500° F.,whereas the brine samples containing the scavenger of only erythorbateturned brown and opaque at 300° F. and remained so at the highertemperatures.

A similar experiment was conducted with a 3.0 lb/bbl oxygen scavenger ofthe invention containing about 10% w/w erythorbate (0.3 lb/bbl) and 90%w/w (2.7 lb/bbl) alkylhydroxylamine solution added to samples of 9.5lb/gal sodium chloride brine. For comparison, oxygen scavengercontaining only 0.25 lb/bbl sodium erythorbate was added to othersamples of 9.5 lb/gal sodium chloride brine. All of the samples wereheated for 16 hours at 300° F. The samples containing the scavenger ofthe invention remained clear and colorless. The samples containing thescavenger having only the sodium erythorbate turned dark and opaque.

These experiments demonstrate a synergistic effect whereby thealkylhydroxylamine is providing a stabilizing effect to the erythorbate.

Further experiments were conducted to test the effectiveness of theoxygen scavenger of the invention in scavenging oxygen in completionbrines. Oxygen scavenger containing only 0.5 lb/bbl erythorbate andoxygen scavenger containing 0.5 lb/bbl scavenger of the inventioncontaining a blend of 0.1 lb/bbl erythorbate and 0.9 lb/bblalkylhydroxylamine solution were added to different samples of 0.5lb/bbl sodium chloride brine, 12.5 lb/bbl sodium bromide brine, 11.0lb/bbl calcium chloride brine and 15.5 lb/bbl zinc bromide/calciumbromide brine. The amount of dissolved oxygen was measured in thesamples over a 24 hour period at room temperature (approximately 70°F.). Room temperature was selected for these experiments because oxygenbecomes less soluble as temperature increases. Also, generally, orusually, oxygen scavengers are added to completion fluids, and dissolvedoxygen levels are measured in completion fluids, before they are placedin a wellbore. A YSI Model 55 Dissolved Oxygen Meter and an ExtechDissolved Oxygen Meter were used for the measurements of dissolvedoxygen. These simple instruments have a probe and a digital readoutsimilar to a pH meter. A colorimetric test kit for dissolved oxygen,such as one offered by CHEMetrics might alternatively be used. Theresults of these experiments are shown in FIGS. 1-4. In each case, thescavenger of the invention provided comparable results to the scavengercontaining only erythrobate.

The amount of oxygen scavenger of the invention needed for such oxygenremoval depends on the amount of oxygen present in the aqueous fluid. Ingeneral, about 0.5 lb/bbl to about 3.0 lb/bbl of the scavenger iseffective for completion operations. The scavenger may be added to thefluid during preparation of the fluid and/or at the beginning or acompletion operation and/or during a completion operation.

Brines comprising the oxygen scavenger of the invention may effectivelybe used in drilling through a producing zone of a high temperaturesubterranean formation, or in working over a wellbore penetrating a hightemperature subterranean formation as well as in traditional operationsfor completing a wellbore in a high temperature subterranean formation,operations such as penetrating a wellbore casing and installing pipesand pumps to facilitate production from the subterranean formationthrough the wellbore. The oxygen scavenger of the invention is similarlyeffective in subterranean formations not having high temperatures (ortemperatures greater than about 275° F.) but its advantages areparticularly appreciated in high temperatures, because the scavengerdoes not break down and a colorless, clear brine remains colorless andclear.

The foregoing description of the invention is intended to be adescription of preferred embodiments. Various changes in the details ofthe described fluids and methods of use can be made without departingfrom the intended scope of this invention as defined by the appendedclaims.

1. A method for reducing the amount of oxygen in an oxygen containingbrine during use in completion operations in a subterranean formation,the method comprising adding to the brine an oxygen scavenger comprisinga blend of erythorbate and alkylhydroxylamine.
 2. The method of claim 1wherein the subterranean formation has temperatures in the range ofabout 275° to about 500° F. and the brine is clear and colorless andremains clear and colorless at temperatures of 275° F.
 3. The method ofclaim 1 wherein the oxygen scavenger keeps the oxygen content in thebrine below about 1 mg/L.
 4. The method of claim 1 wherein the oxygenscavenger keeps the oxygen content in the brine below about 0.5 mg/L. 5.The method of claim 1 wherein the completion operation is drillingthrough a producing zone of the subterranean formation.
 6. The method ofclaim 1 wherein the completion operation comprises completing a welldrilled through a producing zone of the subterranean formation.
 7. Themethod of claim 1 wherein the completion operation comprises a workoverof the well penetrating the subterranean formation.
 8. The method ofclaim 1 wherein the oxygen scavenger comprises erythorbate in an amountranging from 0.01% w/w to 75% w/w and alkylhydroxylamine solution in anamount ranging from 25% w/w to 99.9% w/w.
 9. The method of claim 1wherein the alkylhydroxylamine is selected from the group consisting ofisopropylhydroxylamine, diethylhydroxylamine, tert-butylhydroxylamine,phenylhydroxylamine, cyclohexylhydroxylamine, and benzylhydroxylamine.10. The method of claim 1 wherein ascorbate, ascorbic acid or erythorbicacid is substituted for erythorbate.
 11. An aqueous completion fluid foruse in drilling, completing and/or working over a wellbore penetrating asubterranean formation having temperatures of about 275° F. to about500° F., the fluid having an oxygen scavenger comprising a blend oferythorbate and alkylhydroxylamine.
 12. The completion fluid of claim 11wherein the fluid comprises a clear and colorless brine that remainsclear and colorless during such use.
 13. The fluid of claim 11 whereinthe fluid has an oxygen content of less than about 1 mg/L during suchuse.
 14. The fluid of claim 11 wherein the alkylhydroxylamine isselected from the group consisting of isopropylhydroxylamine,diethylhydroxylamine, tert-butylhydroxylamine, phenylhydroxylamine,cyclohexylhydroxylamine, and benzylhydroxylamine.
 15. The fluid of claim11 wherein ascorbate, ascorbic acid or erythorbic acid is substitutedfor erythorbate.
 16. An oxygen scavenger for completion fluidscomprising a blend of erythorbate and alkylhydroxylamine.
 17. The oxygenscavenger of claim 16 wherein the blend comprises 0.01% w/w to 75% w/werythorbate and 25% w/w to 99.9% w/w alkylhydroxylamine solution. 18.The oxygen scavenger of claim 16 wherein the blend maintains stabilityat temperatures in the range of about 275° F. to about 500° F.
 19. Theoxygen scavenger of claim 16 wherein the alkylhydroxylamine is selectedfrom the group consisting of isopropylhydroxylamine,diethylhydroxylamine, tert-butylhydroxylamine, phenylhydroxylamine,cyclohexylhydroxylamine, and benzylhydroxylamine.
 20. The oxygenscavenger of claim 16 wherein ascorbate, ascorbic acid or erythorbicacid is substituted for erythorbate.
 21. A method of completing awellbore penetrating a subterranean formation comprising employing acompletion fluid comprising a clear, colorless brine and an oxygenscavenger containing erythorbate and alkylhydroxlyamine.
 22. The methodof claim 21 wherein the wellbore comprises casing and the method furthercomprises perforating the casing and setting tubing in the wellbore. 23.The method of claim 21 wherein the brine is used for drilling through aproducing zone of the subterranean formation.
 24. The method of claim 21wherein the brine is used for working over the wellbore.
 25. The methodof claim 21 wherein the alkylhydroxylamine is selected from the groupconsisting of isopropylhydroxylamine, diethylhydroxylamine,tert-butylhydroxylamine, phenylhydroxylamine, cyclohexylhydroxylamine,and benzylhydroxylamine.
 26. The method of claim 21 wherein ascorbate,ascorbic acid or erythorbic acid is substituted for erythorbate.